TW201300444A - Film, laminated film, scratch-resistant film and article - Google Patents

Abstract

The invention relates to a film which is excellent in scratch restoring properties, stain resistance, weatherability, chemical resistance, flex resistance and impact resistance, and is useful as a scratch-resistant film or a decoration film. The film of the invention includes a crosslinking substance which has a composition containing a vinyl compound copolymer and a polyisocyanate, wherein the vinyl compound copolymer includes the following monomer units: (A) a vinyl compound not containing a hydroxyl (a mol%); (B) a vinyl compound having a chain or branched alkyl containing hydroxyl and having 1 to 6 carbons (b mol%); and (C) a vinyl compound having a following formula (c mol%): CH2=C(R)-COO-Y (c mol%). The ''a'' to the ''c'' satisfy ''a+b+c=100'' and following formulas (1) and (2): the formula (1) is ''3 (b+c) /4 ≤ a ≤ 4 (b+c) '', and the formula (2) is ''4c/3 ≤ b ≤ 40c''.

Description

Scratch resistant film

The present invention is directed to a film that is used as a means of applying a coating directly to an article for surface protection or decoration of the article. In particular, there is a film for surface protection or decoration of a white goods product such as an exterior part of a car, a wall material, a floor board, and a refrigerator.

In the past, in order to impart abrasion resistance, weather resistance, durability, stain resistance, corrosion resistance, and creativity to an exterior portion such as a door sash of an automobile, melamine was directly coated according to the material of the member. A curable resin coating material such as a resin, an isocyanate resin, or a urethane resin.

In addition, a hard coat paint such as an ultraviolet curable acrylic resin is directly applied to a home appliance frame or the like to impart functions such as scratch resistance, durability, stain resistance, and creativity.

However, such direct coating has the following problems: multiple steps of masking, coating, hardening, finishing, etc. of the non-coated surface; it is necessary to carry out the work environment or safety and hygiene management to cope with the solvent of the coating; Skilled to achieve uniform and defect-free coating; spray coating is limited in terms of creativity. Further, the ultraviolet curable hard coat paint has a problem that it is likely to cause deterioration due to ultraviolet rays, and satisfactory weather resistance cannot be obtained.

Therefore, direct coating using a film cosmetic material instead of a coating material has been proposed (Patent Document 1). The use of the film cosmetic material solves the problem of direct coating Problems such as industriality, environmental safety, and creativity, but scratch resistance, weather resistance, durability, stain resistance, and corrosion resistance are not sufficient.

Further, as a surface coating material having improved scratch resistance, a composition containing a compound having a decane structure is widely used. The reason for this is that the above compound imparts lubricity to the surface of the coating material and lowers the friction coefficient, whereby the scratch resistance of the coating material can be further improved. However, since the compound having a decane structure has low compatibility with other components and has low miscibility, there is a problem that bleed out and the stain resistance is lowered. A coating film material obtained by curing a copolymer having a polydimethyl siloxane partial portion has also been proposed (Patent Document 2). However, since the coating material also has a decane structure, the stain resistance is still insufficient. .

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-118061

[Patent Document 2] Japanese Patent No. 3999111

An object of the present invention is to provide a film which is useful as a means for directly coating a coating material for the purpose of surface protection or decoration of articles, and which is excellent in scratch resistance and stain resistance.

The present inventors have found that in the film including the crosslinked product of the composition containing the vinyl compound copolymer and the polyisocyanate, the above copolymer includes a specific three kinds of monomer units, thereby having no polydimethyl siloxane. The present invention has been achieved by a structure in which the oxetane structure is excellent in scratch resistance, particularly in scratch recovery, and excellent in stain resistance.

Further, the term "scratch recovery" refers to a property in which the film is elastically deformed immediately when an external pressure is applied to the surface of the film without being easily broken, and after the external pressure is removed, the deformation is restored in the form of plastic deformation without remaining.

That is, the present invention is a film comprising a crosslinked product comprising a composition of a vinyl compound copolymer and a polyisocyanate, wherein the vinyl compound copolymer comprises the following monomer units: (A) a hydroxyl group-free vinyl group a compound (a mol%); (B) a vinyl compound having a hydroxyl group-containing linear or branched alkyl group and having a carbon number of 1 to 6 (b mol%); and (C) having Vinyl compound of the formula (c mol%): CH ₂ =C(R)-COO-Y

[here, R is H or CH ₃ , Y is a linear or branched saturated hydrocarbon group having a hydroxyl group at the terminal, and Y may optionally have a ring-opening lactone group (-CO-(CH ₂ ) _n -O) - where n is an integer from 4 to 6), a carbonate group (-O-CO-O-), an ester group (-CO-O-), an ether group (-O-), and an urethane group (-NH-CO-O-) one or more groups in the group consisting of 12 to 120 carbon atoms]; and the above a~c is a+b+c=100 and satisfies the following formula ( 1) and (2): 3(b+c)/4≦a≦4(b+c).........(1)

4c/3≦b≦40c.........(2).

Further, the present invention provides a laminated film comprising the above film on at least one side of a thermoplastic resin film.

The film and the laminated film of the present invention exhibit the viscoelastic behavior of the voigt model, so that the scratch recovery property is excellent and the stain resistance is excellent, and the weather resistance, chemical resistance, bending resistance, and impact resistance are further improved. Since it is also excellent, it is useful as a means for direct application of a coating material on the surface of an article, for example, a wall surface, a home appliance, an automobile part, etc., for example, as a scratch-proof film or a decorative film.

The film of the present invention includes a crosslinked product of a composition containing a vinyl compound copolymer and a polyisocyanate, and the copolymer includes the following monomer units (A) to (C).

Monomer (A)

The monomer (A) is a vinyl compound having no hydroxyl group. Examples of the monomer (A) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylic acid-2. -ethylhexyl ester, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-stearyl (meth)acrylate, and (meth)acrylic acid such as lauryl (meth)acrylate Ester; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether; aromatic vinyl compounds such as styrene and α-methylstyrene a cyano group-containing vinyl compound such as acrylonitrile or methacrylonitrile; a vinyl carboxylate such as vinyl acetate; a vinyl compound containing a halogen element such as vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride; Rings such as glycidyl (meth)acrylate and allyl glycidyl ether a vinyl compound of an oxy group; a carboxyl group-containing vinyl compound such as acrylic acid or methacrylic acid; and a fluorenyl group-containing vinyl compound such as (meth) acrylamide. Among them, preferred are methyl (meth)acrylate, ethyl (meth)acrylate and n-butyl (meth)acrylate.

Monomer (B)

The monomer (B) is a vinyl compound having a linear or branched alkyl group having a hydroxyl group, and the alkyl group has a carbon number of 1 to 6, preferably 2 to 4. Examples of the monomer (C) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and 4-hydroxy acrylate. Butyl ester, 4-hydroxybutyl methacrylate, hydroxyethyl acrylamide and allyl alcohol, among them, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferred.

Monomer (C)

The monomer (C) is a vinyl compound having the formula: CH ₂ =C(R)-COO-Y.

R is H or CH ₃ , Y is a linear or branched saturated hydrocarbon group having a hydroxyl group at the terminal, and Y may optionally have a ring-opening lactone group (-CO-(CH ₂ ) _n -O-, here) n is an integer from 4 to 6), a carbonate group (-O-CO-O-), an ester group (-CO-O-), an ether group (-O-), and a urethane group (-NH-) One or more groups of the group consisting of CO-O-) (hereinafter sometimes referred to as "open-loop lactone group") have 12 to 120 carbon atoms. When the carbon number of Y is too small, the obtained film has poor scratch recovery properties, and if it is too large, the stain resistance is poor. The carbon number of the above alkyl group is preferably from 25 to 90, more preferably from 36 to 90, and still more preferably from 40 to 90.

The monomer (C) is obtained, for example, by dehydration condensation of (meth)acrylic acid with a long-chain diol, and the long-chain diol is a long-chain diol having a hydroxyl group at both terminals represented by the formula OH-Y, for example Long-chain diol with a molecular weight of 202 to 1714 (carbon number 12 to 120).

Y may have the above-mentioned ring-opening lactone group or the like as needed. It is preferable that such a base is easy to control the carbon number of Y. More preferably, Y has a polylactone structure and/or a polycarbonate structure. In the case where Y is branched, a ring-opening lactone group or the like is more preferably present in the main chain than in the side chain. In addition, when Y has a ring-opening lactone group or the like, the carbon number of Y includes the number of carbons contained in the above-mentioned ring-opening lactone group or the like.

The monomer (C) having a ring-opening lactone group is obtained, for example, by dehydration condensation of (meth)acrylic acid with polycaprolactone diol. The above dehydration condensation can be carried out in accordance with a known method by, for example, an organic solvent such as benzene or toluene, an acid catalyst such as p-toluenesulfonic acid, and a polymerization inhibitor such as hydroquinone or methyl hydroquinone. Heat back together. Examples of the polycaprolactone diol include Placcel 205 (carbon number: 26), Placcel 210 (carbon number: 50), and Placcel 220 (carbon number: 104) manufactured by DAICEL Chemical Industry Co., Ltd. Further, as a commercially available example of the monomer (C) having a polyopening lactone structure in Y, for example, Placcel FM5 manufactured by Daicel Chemical Industry Co., Ltd. (5 mol of caprolactone plus hydroxyethyl methacrylate) may be mentioned. Compound, CH ₂ =C(CH ₃ )-COO-C ₂ H ₄ -O-(CO-C ₅ H ₁₀ -O) ₅ -H, Y has a carbon number of 32) and Placcel FA10L (hydroxyethyl acrylate) 10 mol of caprolactone adduct, CH ₂ =CH-COO-C ₂ H ₄ -O-(CO-C ₅ H ₁₀ -O) ₁₀ -H, Y has a carbon number of 62).

Further, a monomer (C) having a polycarbonate structure can be produced by dehydration condensation of (meth)acrylic acid with a polycarbonate diol. Examples of the polycarbonate diol include Placcel CD205 (carbon number: 27), Placcel CD210 (carbon number: 48), and Placcel CD220 (carbon number: 97) manufactured by Daicel Chemical Industry Co., Ltd.

Blemmer PP-800 (CH ₂ =CH-COO-(C ₃ H ₆ -O) ₁₃ -H, polypropylene glycol monoacrylate) manufactured by Nippon Oil Co., Ltd. can also be used as the monomer (C).

The vinyl compound copolymer of the present invention is obtained by copolymerization of the above monomers (A) to (C). When the amounts of the monomer (A) to the monomer (C) are respectively set to a mol%, b mol%, and c mol%, they must be a+b+c=100 and satisfy the following formula (1) and formula ( 2).

3(b+c)/4≦a≦4(b+c)............(1)

4c/3≦b≦40c.........(2)

The formula (1) represents the relationship between the molar amount (a) of the hydroxyl group-free monomer (A) and the total molar amount (b+c) of the hydroxyl group-containing monomer (B) and the monomer (C). Since a+b+c=100, if the relational expression of b+c=100-a is used, the formula (1) means 42.9≦a≦80. Therefore, 20≦b+c≦57.1.

With respect to the formula (1), when a>4 (b+c) (that is, when a>80), the crosslinking density is too low, and the stain resistance or heat resistance, weather resistance, and chemical resistance are lowered. When 3(b+c)/4>a (that is, when a<42.9), the crosslinking density becomes too high, and a hardened film which is straight and vitreous is formed, so that the scratch recovery property is not exhibited. Preferably, the formula (1) is 5(b+c)/6≦a≦5(b+c)/2. If the relation b+c=100-a is used, it means 45.5≦a≦71.4. Therefore, 28.6≦b+c≦54.5.

Formula (2) represents the relationship between the hydroxyl group-containing monomer (B) and the monomer (C) molar amount. With respect to the formula (2), when 4c/3>b, that is, when the amount of the monomer (B) is too small or the amount of the monomer (C) is too large, the crosslinking density becomes too low, stain resistance or heat resistance, and weather resistance. Sex and chemical resistance decreased. When b>40c, that is, when the amount of the monomer (B) is too large or the amount of the monomer (C) is too small, the crosslinking density becomes too high, and a rigid and glassy cured film is formed, so that the scratch recovery is not exhibited. Sex. In addition, sometimes the bending resistance or impact resistance is also lowered. Preferably, b and c satisfy 8c/5≦b≦8c, and more preferably 2c≦b≦4c.

The above vinyl compound copolymer is usually produced by solution polymerization. Examples of the solvent for solution polymerization include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, propyl acetate and isobutyl acetate. An ester solvent such as butyl acetate or an alcohol solvent such as ethanol, isopropyl alcohol, butanol or isobutanol may be used alone or as a mixed solvent of two or more kinds. A polymerization initiator such as benzammonium peroxide, lauryl peroxide, cumene hydroperoxide or azobisisobutyronitrile may be used as needed. The polymerization temperature is preferably from 60 ° C to 160 ° C, and the reaction time is preferably from 5 hours to 15 hours.

The obtained vinyl compound copolymer is then mixed with a polyisocyanate, and the obtained mixed coating material is applied onto the surface of the thermoplastic resin film, and crosslinked at room temperature or by heating, whereby the laminated film of the present invention can be obtained. . Further, the film of the present invention is obtained by peeling off a thermoplastic resin film from the above laminated film.

The coating method is not particularly limited, and a known web coating method can be used. Specific examples thereof include roll coating, gravure coating, reverse roll coating, roll coating, spray coating, air knife coating, and die coating. The thickness of the coating film is preferably from 10 μm to 100 μm after drying and hardening. If it is too thin, the obtained film of the present invention may not exhibit scratch recovery properties, and if it is too thick, there may be a problem that the coating material flows during coating or the cost is unnecessarily increased.

The polyisocyanate is a compound having a structure of -N=C=O in the molecule, and specific examples thereof include methylenebis-4-cyclohexyl isocyanate, toluene diisocyanate trimethylolpropane adduct, and hexamethylene diene. Trimethylolpropane adduct of isocyanate, trimethylolpropane adduct of isophorone diisocyanate, isomeric cyanurate of toluene diisocyanate, isomeric cyanide of hexamethylene diisocyanate a polyisocyanate such as an acid ester, an isomeric cyanurate of isophorone diisocyanate or a biuret of hexamethylene diisocyanate, or a urethane crosslinking such as a blocked isocyanate of the above polyisocyanate Agent. Preferred examples thereof include methylene bis-4-cyclohexyl isocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, and hexa A polyisocyanate such as a hetero-cyanate of methyl diisocyanate, a meta-isocyanate of isophorone diisocyanate, or a biuret of hexamethylene diisocyanate. In addition, when cross-linking, A catalyst such as dibutyltin dilaurate or dibutyltin diethylhexanoate may be added as needed.

The amount of the polyisocyanate is such that the molar number of the hydroxyl group in the vinyl compound copolymer is preferably from 1:0.7 to 1:1.4, more preferably 1:0.9. 1:1.2. If the amount of isocyanate is too small, stain resistance or weather resistance may be lowered. Further, when the amount of isocyanate is too large, the scratch recovery property or the bending resistance may be lowered.

Crosslinking can be carried out by drying at room temperature or by heating and drying. For example, drying at room temperature can be carried out for 6 hours to 1 week. Heating and drying can be carried out at 40 ° C ~ 300 ° C for 5 seconds ~ 120 minutes. The drying temperature or time is desirably selected in accordance with the properties of the thermoplastic resin film to which the mixed coating material is applied, and may be combined with heat drying and room temperature drying, as the case may be. Further, when the thermoplastic resin film having a low softening point is heated and dried, the thermoplastic resin film may be softened and broken during the drying process, or may cause defects such as wrinkles and shrinkage. In order to prevent such a problem, the thermoplastic resin film may be suitably fixed to a support such as a metal or glass, a ceramic, a thermosetting resin or a thermoplastic resin having a high softening point, and then the coating or drying of the mixed coating material may be carried out. .

Examples of the thermoplastic resin film to be coated with a coating material include polyvinyl chloride resin, polyester having low crystallinity, low crystallinity or crystallinity, polyolefin such as polypropylene or polyethylene, and acrylonitrile-butadiene-styrene. a copolymer resin (ABS resin) or a styrene resin such as a styrene-ethylene-butadiene-styrene copolymer or a hydride thereof, a thermoplastic resin such as polyamine, acrylic acid, polycarbonate, or polyurethane Membranes, including unstretched films, uniaxially stretched films, and biaxial Stretch film. Particularly preferred is an unstretched film of a polyvinyl chloride resin or a non-crystalline polyester resin, or a stretched crystalline polyester film. In the case where the film of the present invention is obtained by peeling off the thermoplastic resin film from the laminated film obtained by applying the coating material onto the thermoplastic resin film, it is preferred to subject the coated surface of the thermoplastic resin film to a release treatment in advance.

The thickness of the thermoplastic resin film is not particularly limited and is usually from 20 μm to 500 μm, and in consideration of applications for vacuum forming, film press forming, air compression press forming, in-mold forming, or insert molding, which will be described later, It is preferably 75 μm to 300 μm.

In addition, when embossing is performed on the surface of the laminated film of the present invention opposite to the thermoplastic resin film (that is, the surface of the coating film) in order to impart creativity or the like, since the coating film has elastic deformation characteristics, it is possible The embossing process becomes difficult, and the thickness of the thermoplastic resin film is set to 80 μm to 300 μm by setting the thickness of the coating film to 10 μm to 30 μm, and the embossing roll having a surface roughness Rz of 20 μm or more is used. Pressing is performed to obtain a good embossed shape.

The film and the laminated film of the present invention are excellent in abrasion recovery property and stain resistance, and also excellent in weather resistance, chemical resistance, bending resistance, and impact resistance, and therefore, instead of directly applying a coating material to the surface of the article, It is useful, for example, as a scratch-resistant film or a decorative film. For example, it can be suitably used for automobile parts such as door and window frames, trims, fenders, bumpers, housings or information display parts of home appliances, wall materials or floor boards of buildings, furniture products, etc. s surface.

Attaching the film or laminate film of the present invention to, for example, wall materials, flooring materials, When a planar member such as an image pattern or a car door sash is used, an adhesive layer or an adhesive layer may be provided on one surface of the film of the present invention or the thermoplastic resin film of the laminated film of the present invention. And cut into the desired shape and attach it. At the time of attachment, in order to prevent air from entering between the film or the laminated film of the present invention and exposing and damaging the appearance, it is preferable to provide a groove for removing air on the surface of the adhesive layer or the adhesive layer. . On the other hand, if such a venting groove is provided, the appearance of the portion corresponding to the groove on the surface of the film of the present invention may be defective in appearance, and in order to prevent the appearance defect, the design of the vent groove, the groove The width is preferably from 10 μm to 200 μm, more preferably from 50 μm to 150 μm. Further, the depth of the groove is preferably from 5 μm to 50 μm, more preferably from 10 μm to 30 μm, and the cross-sectional shape thereof is semicircular. Further, in order to efficiently discharge the bubbles so as not to cause an appearance defect, it is recommended to arrange the grooves in such a manner that when the surface of the adhesive layer having the grooves is viewed from the vertical direction, the adhesive layer separated by the grooves is an equilateral triangle, a regular square, A repeating structure of a diamond or a regular hexagon.

Further, the film or laminated film of the present invention is used for surface protection of a three-dimensional and complicated shape member such as a casing of a home electric appliance, an instrument panel, a shift knob, and an assault grip. Or in the case of decoration, it can be integrally formed by vacuum forming, film press forming, air compression press forming, in-mold forming, insert molding, or the like. In the case of integrally molding, it is preferred to provide an adhesive layer or an adhesive layer on one surface of the film of the present invention or the thermoplastic resin film of the laminated film of the present invention. In the case of vacuum forming, it is necessary to follow the complicated shape of the member, and therefore the glass transition point of the thermoplastic resin film It is preferably 60 ° C to 130 ° C, and specifically, a film of an acrylic resin, a polyvinyl chloride resin, a polyester resin, and an acrylonitrile-butadiene-styrene copolymer resin. Further, since the laminated film is stretched in the vacuum forming, the film of the present invention is preferably provided in such a manner that the isocyanate group of the polyisocyanate is from 0.7 equivalent to 1.2 equivalents per equivalent of the hydroxyl group of the vinyl compound copolymer.

[Example]

Hereinafter, the present invention will be described by way of examples, but the invention is not limited thereto.

Example 1

100 parts by mass of methyl isobutyl ketone was placed in a 500 ml flask under a nitrogen atmosphere, and the temperature was raised to 100 °C. Further, 100 parts by mass of the mol% of the monomer (A), the monomer (B), and the monomer (C-1) shown in Table 1 were mixed (that is, the monomer (A) was 29 parts by mass, and the monomer (B). 15 parts by mass and a monomer (C-1) 57 parts by mass) and 2 parts by weight of 2,2'-azobisisobutyronitrile (manufactured by Japan Finechem Co., Ltd., ABN-R), and the mixture was dropped for 3 hours. Add to 100 ° C in methyl isobutyl ketone. Further, heating and refluxing were carried out for 6 hours to obtain a target copolymer (solid content: 50%).

100 parts by mass of the obtained vinyl compound copolymer and 34 parts by mass of polyisocyanate were mixed, and the obtained coating material was applied to polyester manufactured by Toray Film Processing Co., Ltd. so that the coating film thickness after drying became 50 μm. After the release treatment surface of the film "Cerapeel 38" (trade name), it was heated at 150 ° C for 30 minutes, and further allowed to stand at room temperature for 24 hours to form a coating film. The coating film was peeled off from Cerapeel 38 to obtain a target film (A). The resulting film The following tests (1) to (13) were performed. The results are shown in Table 1.

Example 2 to Example 13 and Comparative Example 1 to Comparative Example 6

Each monomer shown in Table 1 was used in an amount of mol% shown in Table 1 (the number in parentheses is a part by mass), and copolymerization was carried out in the same manner as in Example 1 to obtain 100 parts by mass of the obtained vinyl compound copolymer. The amount (parts by mass) of the polyisocyanate shown in Fig. 1 was mixed, and the obtained coating material was applied to a polyester film "Emblet S50" (trade name) manufactured by Unitika so as to have a coating film thickness after drying of 20 μm. After the single surface, the film was heated at 150 ° C for 30 minutes, and further allowed to stand at room temperature for 24 hours to form a coating film, thereby obtaining a target laminated film (B). The obtained laminated film was subjected to the following tests (1) to (13). The results are shown in Table 1.

The materials used are as follows.

Monomer (A): manufactured by Mitsubishi Rayon Co., Ltd., methyl methacrylate

Monomer (B): manufactured by Nippon Shokubai Co., Ltd., 2-hydroxyethyl methacrylate, hydroxyl group-containing alkyl group having 2 carbon atoms

Monomer (C-1): Placcel FA10L manufactured by Daicel Chemical Industry Co., Ltd., 10 mol caprolactone adduct of hydroxyethyl acrylate, Y has a carbon number of 62 and a molecular weight of 1256.

Monomer (C-2): Placcel FM5 manufactured by Daicel Chemical Industry Co., Ltd., 5 mol caprolactone adduct of hydroxyethyl methacrylate, Y has a carbon number of 32 and a molecular weight of 700.

Monomer (C-3): Placcel FM3 manufactured by Daicel Chemical Industry Co., Ltd., 3 mol caprolactone addition of hydroxyethyl methacrylate , Y has a carbon number of 20 and a molecular weight of 472

Monomer (C-4): Placcel CD210 (polycarbonate diol HO-(C ₆ H ₁₂ -O-CO-O) ₆ -C ₆ H ₁₂ -OH) manufactured by Daicel Chemical Industry Co., Ltd. and acrylic acid Dehydrated condensate, Y has a carbon number of 48 and a molecular weight of 1036

Monomer (C-5): Placcel CD220 (polycarbonate diol, HO-(C ₆ H ₁₂ -O-CO-O) ₁₃ -C ₆ H ₁₂ -OH) manufactured by Daicel Chemical Industry Co., Ltd. a dehydrated condensate of acrylic acid, Y has a carbon number of 97 and a molecular weight of 2044

Monomer (C-6): A compound prepared by the method described below, Y has a carbon number of 46 and a molecular weight of 1002.

Comparative monomer (C): Dehydrated condensate of Placcel 230 (polycaprolactone diol, carbon number 158) and acrylic acid manufactured by Daicel Chemical Industry Co., Ltd., Y has a carbon number of 158 and a molecular weight of 3096.

Alkoxylate compound: X-22-2426 manufactured by Shin-Etsu Chemical Co., Ltd., single-end methacrylic acid modified polydimethyl siloxane, molecular weight: about 14,000

Polyisocyanate: Coronate HX manufactured by Japan Polyurethane Industry, 100% solid content, 21.3% by mass NCO content

Preparation of monomer (C-6)

Placcel FM2D (2 mol caprolactone adduct of hydroxyethyl methacrylate, molecular weight 358) manufactured by Daicel Chemical Industry Co., Ltd. and adipic acid (molecular weight 146) were dehydrated and condensed using an acid catalyst. Synthetic terminal carboxylic acid modified methacrylate. Then, Placcel 205 (caprolactone tetramer diol, H-{O(CH ₂ ) ₅ CO} ₂ -) manufactured by Daicel Chemical Industry Co., Ltd. was added to the terminal carboxylic acid-modified methacrylate. O-CH ₂ -O-CH ₂ -O-{CO(CH ₂ ) ₅ O} ₂ -H, molecular weight 534), dehydration condensation using an acid catalyst to obtain a terminal hydroxyl group-containing methacrylate monomer ( C-6).

test

(1) Scrap recovery

The film (A) or the laminated film (B) obtained above was cut into a length of 150 mm × a width of 75 mm to prepare a test piece, which was placed on a glass plate. In the case of the laminated film (B), it is placed so that the coating film surface becomes a surface. Using a four-row brass brush manufactured by Nakaya-Brush Industries (with a load of 500 gf), the surface of the test piece was rubbed back and forth 10 times in a single pass of 100 mm, and the brass brush was quickly removed and observed until the surface adhered. The time until the bruise disappears.

○: The abrasion disappeared within 1 minute.

△: The abrasion disappeared within 1 minute to 24 hours.

×: Even after 24 hours or more, the abrasion did not disappear.

(2) abrasion resistance to friction

The film (A) or the laminated film (B) obtained above was cut into a length of 200 mm × a width of 25 mm to prepare a test piece, which was placed in a vibration tester of JIS L 0849. In the case of the laminated film (B), it is placed so that the coating film surface becomes a surface. Then, after the No. 3 muslin cloth was attached to the friction terminal of the Yu Xuezhen test machine in a stack of five layers, a load of 500 gf was applied and the surface of the test piece was reciprocated 100 times to confirm the degree of scratching of the surface thereafter.

◎: No scratches were observed.

○: A slight scratch of less than 10 pieces was observed on the surface of the coating film.

△: 10 or more slight scratches were observed on the surface of the coating film.

×: Obvious scratches were observed on the entire surface of the coating film.

(3) Bending resistance

The film (A) or the laminated film (B) obtained above was cut into a size of 100 mm × 50 mm, and attached to an aluminum plate having a thickness of 0.3 mm using a double-sided tape No. 500A manufactured by Nitto Denko as a test piece. In the case of the laminated film (B), the coating film surface is attached to the surface. A JIS K 5600-5-1 type 1 bending test apparatus equipped with a mandrel having a diameter of 2 mm was used for the test piece, and the film surface was bent outward at a uniform speed for 2 seconds. Fold it to 180°. After the end of the bending, the coating film was confirmed to be damaged at a center portion of 30 mm in the center of the bent portion.

○: No damage occurred.

△: No breakage occurred, but the bent portion became white.

×: A breakage occurred.

(4) Impact resistance

The film (A) or the laminated film (B) obtained above was cut out to a size of 100 mm × 50 mm, and attached to an aluminum plate of 150 mm × 75 mm × 1 mm using a double-sided tape No. 500A manufactured by Nitto Denko. As a test piece. In the case of the laminated film (B), the coating film surface is attached to the surface. The test piece was placed in a DuPont-type impact tester in which an iron ball of φ1/4 inch was attached according to JIS K 5600-5-3 with the coating film facing up, and the weight of the load of 300 gf was 20 After the height of cm is dropped and an impact is applied, the coating film is evaluated. No damage.

○: No damage occurred.

×: A breakage occurred.

(5) Water resistance

Using the same test piece as the above test (4), it was immersed in warm water of 40 ° C for 168 hours, and then taken out, and the appearance of the coating film was visually evaluated within 1 hour based on the following criteria.

○: No change was seen.

△: There was a small degree of swelling, peeling, or breakage that could not be confirmed by the naked eye but was confirmed when using a microscope, and a slight gloss drop or dirt caused by the above was visually confirmed.

×: Expansion, peeling or breakage was confirmed by the naked eye.

(6) Moisture resistance

Using the same test piece as in the above test (4), it was placed in a constant temperature and humidity chamber at 50 ° C and 95% RH for 168 hours, and then taken out, and the coating was visually evaluated within 1 hour according to the same evaluation standard as the test (5). The appearance of the film.

(7) Heat resistance

Using the same test piece as the above test (4), it was placed in a gear oven at 100 ° C for 1 hour, taken out, and further allowed to stand at room temperature for 1 hour or more, and then visually evaluated based on the same evaluation criteria as in Test (5). The appearance of the film.

(8) Acid resistance

Using the same test piece as the above test (4), 2 ml of 10% dilute sulfuric acid was added dropwise thereto and allowed to stand at room temperature for 24 hours, and then sufficiently washed with water. Will After the test piece was further allowed to stand at room temperature for 1 hour or more, the appearance of the coating film was visually evaluated based on the same evaluation criteria as in the test (5).

(9) Alkali resistance

Using the same test piece as the above test (4), 2 ml of a 5% sodium carbonate aqueous solution was added dropwise thereto, and the mixture was allowed to stand at 40 ° C for 6 hours, and then sufficiently washed with water. After the test piece was further allowed to stand at room temperature for 1 hour or more, the appearance of the coating film was visually evaluated based on the same evaluation criteria as in the test (5).

(10) Gasoline resistance

Using the same test piece as the above test (4), 2 ml of No. 1 gasoline according to JIS K 2202 was added thereto and left at room temperature for 24 hours, and then sufficiently washed with water. After the test piece was further allowed to stand at room temperature for 2 hours or more, the appearance of the coating film was visually evaluated based on the same evaluation criteria as in the test (5).

(11) Alcohol resistance

Using the same test piece as the above test (4), 2 ml of ethanol was added dropwise thereto and allowed to stand at room temperature for 24 hours, and then sufficiently washed with water. After the test piece was further allowed to stand at room temperature for 24 hours or more, the appearance of the coating film was visually evaluated based on the same evaluation criteria as in the test (5).

(12) Weather resistance

Using the same test piece as the above test (4), it was exposed to a daylight type weatherproof machine for 2,000 hours, and then sufficiently washed with water. After the test piece was further allowed to stand at room temperature for 24 hours or more, the appearance of the coating film was visually evaluated based on the same evaluation criteria as in the test (5).

(13) Pollution resistance

Prepare two test pieces identical to the above test (4), and test the test pieces The tablets were placed in the outdoor for 180 days and 360 days, respectively, and washed thoroughly. After the test pieces were further allowed to stand at room temperature for 24 hours or more, the appearance of the coating film was visually evaluated based on the following evaluation criteria.

○: No change in appearance was observed for any of the test pieces.

△: A test piece placed only for 360 days was confirmed to have a decrease in gloss, swelling, peeling, and the like.

×: The gloss reduction, swelling, peeling, and the like were confirmed regardless of which test piece.

(14) Operational

The film (A) or the laminated film (B) was cut out to 100 mm × 25 mm, and the distance between the jigs was set to 50 mm, and it was mounted in a Tensilon RTG-1310 tensile tester manufactured by A & D to stretch When the tensile test was carried out at a speed of 200 mm/min, a 10% modulus value was measured. The smaller the value, the higher the possibility of breakage during operation and the worse the operability.

○: 10% modulus value is 10 N/25 mm or more

△: 10% modulus value is 1 N/25 mm or more and less than 10N/25 mm

×: 10% modulus value is less than 1 N/25 mm

As shown in Table 1, the film and the laminated film of the present invention are excellent in scratch recovery property and stain resistance, and are also excellent in weather resistance, chemical resistance, bending resistance, and impact resistance.

On the other hand, in Comparative Example 1 in which a does not satisfy the formula (1) and the amount of the monomer (A) is too large, the chemical resistance, the weather resistance, and the stain resistance are inferior, and the amount of the monomer (A) is too small. In the middle, the abrasion is poorly restored. In Comparative Example 3 in which b and c did not satisfy the formula (2) and the amount of the monomer (B) was too large, the scratch recovery property, the bending resistance and the impact resistance were inferior, and the amount of the monomer (B) was too small. , poor pollution resistance. In Comparative Example 5 in which a monomer having a hydroxyl group-containing alkyl group having more carbon atoms than the range of the present invention was used as the monomer (C), the stain resistance was poor. In Comparative Example 6 in which the vinyl compound copolymer had a decane structure, the stain resistance was poor.

Example 14

100 parts by mass of a vinyl chloride resin (manufactured by Shin-Etsu Chemical Co., Ltd., polymerization degree: 1100), and a polyester-based plasticizer (manufactured by Kao Co., Ltd., HA-5 (trade name)) 20 mass by a calendering machine A film of a composition of 5 parts by mass of carbon black (manufactured by Mitsubishi Chemical Corporation, MCF #1000 (trade name)) was used to obtain a substrate film (thickness: 100 μm). A film obtained in the same manner as in Example 1 except that the coating film thickness was 15 μm was bonded to one surface of the base film by a metal roll to obtain a laminated film. Then, a satin embossing roll having a surface roughness Rz of 30 μm was pressed at 5 kgf/cm ² at 100 ° C on the surface of the coating film to obtain an embossed film 1 .

Example 15

The coating film thickness was 25 μm in Example 14, in addition to the examples. The embossed film 2 was obtained in the same manner.

Example 16

The embossed film 3 was obtained in the same manner as in Example 14 except that the thickness of the base film was changed to 250 μm in Example 14.

Example 17

In Example 14, 100 parts by mass of PET-G resin (Eastman Chemical Co., Ltd., Easter G6763) and carbon black (manufactured by Mitsubishi Chemical Corporation, MCF #1000 (trade name)) were used in an amount of 5 parts by mass. The embossed film 4 was obtained in the same manner as in Example 14 except that the substrate film (thickness: 100 μm) was produced by an extrusion molding machine.

Reference example 1

The embossed film 5 was obtained in the same manner as in Example 14 except that the surface roughness Rz of the embossing roll was 10 μm.

Reference example 2

An embossed film 6 was obtained in the same manner as in Example 14 except that the thickness of the coating film was changed to 5 μm in Example 14.

Reference example 3

An embossed film 7 was obtained in the same manner as in Example 14 except that the coating film thickness was 40 μm in Example 14.

Comparative Example 7

100 parts by mass of ALLEX26 K-37 (trade name) manufactured by Nippon Chemical Co., Ltd., which is not scratch-resistant, and 10 parts by mass of the ALLEX 26 hardener, as a coating material for obtaining a coating film, and Example 14 The embossed film 8 is obtained in the same manner.

The embossed film 1 to the embossed film 8 obtained above was subjected to the following embossing workability test and the tests of the above (1) and (13). The results are shown in Table 2.

Embossing processability

The surface of the coating film of the obtained embossed film was visually evaluated based on the following evaluation criteria.

○: Embossing was formed on the entire surface of the coating film, and there was no damage or opening of the coating film.

×: The embossing is almost or completely unformed, or the coating film is broken or opened.

Claims (5)

A film comprising a crosslinked product comprising a composition of a vinyl compound copolymer and a polyisocyanate, wherein the vinyl compound copolymer comprises the following monomer units: (A) a vinyl compound having no hydroxyl group (a mol%) (B) a vinyl compound having a hydroxyl group-containing linear or branched alkyl group and having a carbon number of 1 to 6 in the above alkyl group (b mol%); and (C) an ethylene having the following formula; Base compound (c mol%): CH ₂ =C(R)-COO-Y [here, R is H or CH ₃ , and Y is a linear or branched saturated hydrocarbon group having a hydroxyl group at the terminal, and Y may be used as needed Having a compound selected from the group consisting of a ring-opening lactone group (-CO-(CH ₂ ) _n -O-, where n is an integer of 4-6), a carbonate group (-O-CO-O-), an ester group (-CO) -O-), one or more groups in the group consisting of an ether group (-O-) and a urethane group (-NH-CO-O-), and having 12 to 120 carbon atoms]; The above a~c is a+b+c=100 and satisfies the following formula (1) and formula (2): 3(b+c)/4≦a≦4(b+c)...(1) 4c /3≦b≦40c.........(2). The film of claim 1, wherein the monomer sheet is Y in the element (C) has one or more groups selected from the group consisting of a ring-opening lactone group, a carbonate group, an ester group, an ether group, and a urethane group. A laminated film having a film as described in claim 1 or 2 on at least one side of a thermoplastic resin film. A scratch-resistant film comprising the film of claim 1 or 2 or the laminated film of claim 3 of the patent application. An article having a scratch-resistant film as described in claim 4 of the patent application.